A method and structure for forming an enhanced metal capping layer includes forming a portion of a multi-level metal interconnect network over a substrate. In some embodiments, the portion of the multi-level metal interconnect network includes a plurality of metal regions. In some cases, a dielectric region is disposed between each of the plurality of metal regions. By way of example, a metal capping layer may be deposited over each of the plurality of metal regions. Thereafter, in some embodiments, a self-assembled monolayer (SAM) may be deposited, where the SAM forms selectively on the metal capping layer, while the dielectric region is substantially free of the SAM. In various examples, after selectively forming the SAM on the metal capping layer, a thermal process may be performed, where the SAM prevents diffusion of the metal capping layer during the thermal process.